EP1448484A1 - Cleaning method - Google Patents

Cleaning method

Info

Publication number
EP1448484A1
EP1448484A1 EP02803873A EP02803873A EP1448484A1 EP 1448484 A1 EP1448484 A1 EP 1448484A1 EP 02803873 A EP02803873 A EP 02803873A EP 02803873 A EP02803873 A EP 02803873A EP 1448484 A1 EP1448484 A1 EP 1448484A1
Authority
EP
European Patent Office
Prior art keywords
water
microns
salt
citric acid
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02803873A
Other languages
German (de)
French (fr)
Other versions
EP1448484B1 (en
Inventor
Manuela Bosco
Roberto Casonati
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser NV
Original Assignee
Reckitt Benckiser NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser NV filed Critical Reckitt Benckiser NV
Publication of EP1448484A1 publication Critical patent/EP1448484A1/en
Application granted granted Critical
Publication of EP1448484B1 publication Critical patent/EP1448484B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof

Definitions

  • This invention relates to a method of softening water and/or in which the deposition of hard water scale is inhibited.
  • the invention relates in particular to such a method carried out in a domestic environment.
  • the invention also relates to compressed water-softening compositions for such methods in which 50% or more of the particles of citric acid or a salt thereof are greater than 200 microns and 10% or less of the particles of citric acid or a salt thereof are less than 200 microns.
  • Suitable levels of "hardness” are between 150 N and 250 N (the test conditions being set out in the Example section).
  • Suitable levels of "friability” are between 2% and 9% (the test conditions being set out in the Example section) .
  • Suitable "disintegration" times are between 5 seconds and 180 seconds, when place in 11 of gently stirred water.
  • Multi-region compressed compositions are now of interest in being able to provide such advantages as differential release of actives, or delayed release of one region.
  • Developing multi-region compressed compositions is time consuming and expensive due to ingredients reacting to the same physical conditions in different ways, such as moisture or temperature fluctuations. This is may lead to problems at the interface between the regions and the need to prevent separation, which can be caused, for example, by differential expansion. Therefore there is a need to balance the physical properties between the regions even where the composition in each region may be different.
  • the starting point is usually to start by keeping the compositions between the regions as similar as possible.
  • water-softening ingredients are generally highly crystalline and are not easily produced into compressed formulations, such as the citrate and silicates.
  • a compressed composition comprising citric acid, or a salt thereof, in which 45%, or greater than 45%, or greater than 60%, ideally greater than 90%, or at least 95% of the particles have a size of at least 200 microns, 300 microns or 400 microns.
  • 60%, or greater than 45%, of the particles have a size greater than 425 microns or of 425 microns or more.
  • 10% or less of the particles of citric acid or a salt thereof have a particle size of less than 200 microns.
  • An alternative feature of the invention is the use of citric acid, or a salt thereof, in which 60%, preferably greater than 60%, of the particles have a size of at least 425 microns in preparing a compressed water- softening product .
  • a preferred active is a homo or co polymer of the following monomeric units or a salt thereof; an acrylic acid, a maleic acid, a sulfonic acid or a phosphonic acid.
  • a preferred distribution is the weight excess of citric acid or its salt in at least one region is at least 5%, ideally greater than 7%, 10%, 12%, 20%, 50%, 75% or 95% greater than in a second region.
  • Ion exchange agents - such agents include alkali metal (preferably sodium) aluminosilicates either crystalline, amorphous or a mixture of the two.
  • alkali metal preferably sodium
  • Such aluminosilicates generally have a calcium ion exchange capacity of at least 50 mg CaO per gram of aluminosilicate, comply with a general formula:
  • sodium aluminosilicates within the above formula contain 1.5-3.0 Si0 2 units. Both amorphous and crystalline aluminosilicates can be prepared by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion- exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble) .
  • the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, and mixtures thereof.
  • zeolite P described in EP 384070 (Unilever) .
  • Another class of compounds are the layered sodium silicate builders, such as are disclosed in US-A-4464839 and US-A-4820439 and also referred to in EP-A-551375.
  • M denotes sodium or hydrogen
  • x is from 1.9 to 4
  • y is from 0 to 20.
  • Quoted literature references describing the preparation of such materials include Glastechn. Ber. 37,194-200 (1964), Zeitschrift fur Kristallogr. 129, 396- 404 (1969), Bull. Soc . Franc. Min. Crist., 95, 371-382 (1972) and Amer. Mineral, 62, 763-771 (1977) . These materials also function to remove calcium and magnesium ions from water, also covered are salts of zinc which have also been shown to be effective water softening agents .
  • Ion capture agents - agents which prevent metal ions from forming insoluble salts or reacting with surfactants, such as polyphosphate, monomeric polycarbonates, such as citric acid or salts thereof, EDTA, algins, alginates.
  • surfactants such as polyphosphate, monomeric polycarbonates, such as citric acid or salts thereof, EDTA, algins, alginates.
  • Anti-nucleating agents - agents which prevent seed crystal growth such as polycarbonate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates and sulfonates.
  • compositions may be used in ware washing using a machine or a manual method.
  • the compositions may also be used to soften water in other cleaning methods such as hard surfaces, for example using a hand-cloth or mop, and an open vessel, for example a bucket or bowl.
  • the cleaning method could be a method of cleaning a hard surface, for example a window, a tiled surface, shower screen, dirty tableware and kitchenware, a sanitary article, for example a bath, shower screen, lavatory, wash basin or sink, a car or a kitchen worktop.
  • Wi weight of the tablets after one minute of test at 50 rpm
  • Sodium citrate was used of the following granulometry
  • PRODUCT 1000 ⁇ 850 600 ⁇ 425 212 ⁇ 125 ⁇ 63 ⁇ ⁇ 63 ⁇

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)

Abstract

This invention relates to a method of softening water and/or in which the deposition of hard water scale is inhibited. The invention relates in particular to such a method carried out in a domestic environment. The invention also relates to compressed water-softening compositions for such methods in which 50% or greater of the particles of citric acid or a salt thereof are greater than 200 microns and 10% or less of the particles of citric acid or a salt thereof have a particle size of more than 200 microns.

Description

CLEANING METHOD
This invention relates to a method of softening water and/or in which the deposition of hard water scale is inhibited. The invention relates in particular to such a method carried out in a domestic environment. The invention also relates to compressed water-softening compositions for such methods in which 50% or more of the particles of citric acid or a salt thereof are greater than 200 microns and 10% or less of the particles of citric acid or a salt thereof are less than 200 microns.
It is well known that certain metal compounds, notably calcium compounds, when present in water, have a significant effect on the properties of the water. For example, "hard" water containing a significant loading of soluble calcium and magnesium compounds may require a large amount of soap or detergent in order to form a lather. Scale deposits can readily form from such water, for example on heating or pH change or evaporation. These can be encrustations, or watermarks left on evaporation of water droplets from, especially, a shiny surface .
There have been many proposals for removal of metal ions from aqueous solutions. In the industrial context proposals have included filter beds and polymeric filters for capturing heavy metal ions from an aqueous solution flowing within a passageway. Examples are given in EP992238A and GB20869564A. In the domestic context chelating compositions can be added to an aqueous washing solution and these can capture metal ions, such as calcium ions. Examples of chelating compositions are given in EP892040A.
Increasingly popular is the delivery of cleaning and water-softening compositions as compressed compositions, typically a tablet. These are convenient providing a unit dosage which is easily handled. Difficulties arise in the production of such compressed compositions in balancing the needs that the compressed composition is suitably hard and non-friable under transportation conditions but yet is not so compacted that it cannot easily disintegrate. Suitable levels of "hardness" are between 150 N and 250 N (the test conditions being set out in the Example section). Suitable levels of "friability" are between 2% and 9% (the test conditions being set out in the Example section) . Suitable "disintegration" times are between 5 seconds and 180 seconds, when place in 11 of gently stirred water.
Multi-region compressed compositions are now of interest in being able to provide such advantages as differential release of actives, or delayed release of one region. Developing multi-region compressed compositions is time consuming and expensive due to ingredients reacting to the same physical conditions in different ways, such as moisture or temperature fluctuations. This is may lead to problems at the interface between the regions and the need to prevent separation, which can be caused, for example, by differential expansion. Therefore there is a need to balance the physical properties between the regions even where the composition in each region may be different. To aid ease of development the starting point is usually to start by keeping the compositions between the regions as similar as possible.
A particular problem found with producing such a multi-region product is that the water-softening ingredients are generally highly crystalline and are not easily produced into compressed formulations, such as the citrate and silicates.
We have found that for certain common actives in water-softening compositions the distribution of the granulometry of citric acid, or a salt thereof, is important in the manufacture of compressed compositions, in particular water-softening compositions which contain a high proportion of this ingredient. The selected particle size distribution improve binding properties. The resulting compressed composition is in fact more stable and maintains acceptable levels of friability and of disintegration for a longer time. Also the aesthetic of the compressed composition is better.
Therefore we present as a feature of the invention a compressed composition comprising citric acid, or a salt thereof, in which 45%, or greater than 45%, or greater than 60%, ideally greater than 90%, or at least 95% of the particles have a size of at least 200 microns, 300 microns or 400 microns. Preferably 60%, or greater than 45%, of the particles have a size greater than 425 microns or of 425 microns or more. Preferably 10% or less of the particles of citric acid or a salt thereof have a particle size of less than 200 microns. An alternative feature of the invention is the use of citric acid, or a salt thereof, in which 60%, preferably greater than 60%, of the particles have a size of at least 425 microns in preparing a compressed water- softening product .
Additional water-softening actives may also be present as described below. A preferred active is a homo or co polymer of the following monomeric units or a salt thereof; an acrylic acid, a maleic acid, a sulfonic acid or a phosphonic acid.
We have also found that the distribution of citric acid, or its salt, between the regions of the compressed formulation affects the values discussed above. A preferred distribution is the weight excess of citric acid or its salt in at least one region is at least 5%, ideally greater than 7%, 10%, 12%, 20%, 50%, 75% or 95% greater than in a second region.
There are three main types of method of action for water softening actives, described below.
1) Ion exchange agents - such agents include alkali metal (preferably sodium) aluminosilicates either crystalline, amorphous or a mixture of the two. Such aluminosilicates generally have a calcium ion exchange capacity of at least 50 mg CaO per gram of aluminosilicate, comply with a general formula:
0.8-1.5 Na20 . Al203 . 0.8-6 Si02 and incorporate some water. Preferred sodium aluminosilicates within the above formula contain 1.5-3.0 Si02 units. Both amorphous and crystalline aluminosilicates can be prepared by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion- exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, and mixtures thereof. Also of interest is zeolite P described in EP 384070 (Unilever) .
Another class of compounds are the layered sodium silicate builders, such as are disclosed in US-A-4464839 and US-A-4820439 and also referred to in EP-A-551375.
These materials are defined in US-A-4820439 as being crystalline layered, sodium silicate of the general formula
NaMSix02x+ι . YH20
where
M denotes sodium or hydrogen, x is from 1.9 to 4 and y is from 0 to 20. Quoted literature references describing the preparation of such materials include Glastechn. Ber. 37,194-200 (1964), Zeitschrift fur Kristallogr. 129, 396- 404 (1969), Bull. Soc . Franc. Min. Crist., 95, 371-382 (1972) and Amer. Mineral, 62, 763-771 (1977) . These materials also function to remove calcium and magnesium ions from water, also covered are salts of zinc which have also been shown to be effective water softening agents .
2) Ion capture agents - agents which prevent metal ions from forming insoluble salts or reacting with surfactants, such as polyphosphate, monomeric polycarbonates, such as citric acid or salts thereof, EDTA, algins, alginates.
3) Anti-nucleating agents - agents which prevent seed crystal growth, such as polycarbonate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates and sulfonates.
The compositions may be used in ware washing using a machine or a manual method. The compositions may also be used to soften water in other cleaning methods such as hard surfaces, for example using a hand-cloth or mop, and an open vessel, for example a bucket or bowl. Thus, the cleaning method could be a method of cleaning a hard surface, for example a window, a tiled surface, shower screen, dirty tableware and kitchenware, a sanitary article, for example a bath, shower screen, lavatory, wash basin or sink, a car or a kitchen worktop. The invention will now be described, by way of embodiment, with reference to the following examples
Hardness Test
Using a dynamometer with a test piston diameter of 8 mm and a piston speed 30 mm per minute (a machine such as the ERWEKA tablet hardness tester THB 30 may be used) the maximum hardness of the tablet just prior to breakage is recorded for 4 tablets in the same orientation and averaged.
Friability Test
Ten tablets are weighed and placed into a square plastic sample holder of approximate dimensions llOXllOmm square by 170mm long. The sample holder is rotated horizontally along it length at 50 rpm for 1 minute. The tablets are weighed again and the amount of material loss expressed as percentage
% friability index = lOO
where : W0 = initial weight
Wi = weight of the tablets after one minute of test at 50 rpm
Sodium citrate was used of the following granulometry
PRODUCT 1000 μ 850 600 μ 425 212 μ 125 μ 63 μ <63μ
Below is an example of formula in which the use of the above citrate is used.

Claims

1. A compressed composition comprising citric acid, or a salt thereof, in which greater than 45% of the particles have a size of at least 425 microns.
2. A compressed composition comprising citric acid, or a salt thereof, as claimed in claim 1, in which greater than 60% of the particles have a size of greater than 425 microns .
3. A compressed composition comprising citric acid, or a salt thereof, as claimed in claim 1, in which greater than 95% of the particles have a size of at least 200 microns .
4. A compressed composition comprising citric acid, or a salt thereof, as claimed in any claim from 1 to 4 , in which the percentage of particles as defined have a size of at least 300 microns.
5. A compressed composition comprising citric acid, or a salt thereof, as claimed in any claim from 1 to 4 , in which the percentage of particles as defined have a size of at least 400 microns.
6. Use of citric acid, or a salt thereof, in which greater than 60% of the particles have a size of at least 425 microns in preparing a compressed water-softening product .
EP02803873A 2001-11-27 2002-11-27 Cleaning method Expired - Lifetime EP1448484B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0128332 2001-11-27
GB0128332A GB2382343A (en) 2001-11-27 2001-11-27 Water softening composition
PCT/GB2002/005342 WO2003045855A1 (en) 2001-11-27 2002-11-27 Cleaning method

Publications (2)

Publication Number Publication Date
EP1448484A1 true EP1448484A1 (en) 2004-08-25
EP1448484B1 EP1448484B1 (en) 2012-06-13

Family

ID=9926490

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02803873A Expired - Lifetime EP1448484B1 (en) 2001-11-27 2002-11-27 Cleaning method

Country Status (6)

Country Link
EP (1) EP1448484B1 (en)
AU (1) AU2002365310A1 (en)
DE (1) DE20220459U1 (en)
ES (1) ES2386539T3 (en)
GB (1) GB2382343A (en)
WO (1) WO2003045855A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2410496A (en) * 2004-01-31 2005-08-03 Reckitt Benckiser Nv Water softening tablets

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5114647A (en) * 1991-02-01 1992-05-19 Olin Corporation Effervescent tablets having increased disintegration rates
GB2318575A (en) * 1996-10-22 1998-04-29 Unilever Plc Detergent tablet
EP1002041B1 (en) * 1997-07-09 2003-03-05 The Procter & Gamble Company Cleaning compositions comprising an oxidoreductase
GB9821190D0 (en) * 1998-09-30 1998-11-25 Unilever Plc Detergent composition
GB2348884A (en) * 1999-04-13 2000-10-18 Procter & Gamble Light reflecting particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03045855A1 *

Also Published As

Publication number Publication date
GB0128332D0 (en) 2002-01-16
DE20220459U1 (en) 2003-10-02
ES2386539T3 (en) 2012-08-22
WO2003045855A1 (en) 2003-06-05
AU2002365310A1 (en) 2003-06-10
EP1448484B1 (en) 2012-06-13
GB2382343A (en) 2003-05-28

Similar Documents

Publication Publication Date Title
ES2203777T3 (en) PADS TO SOFT THE WATER.
JPS585397A (en) Fiber product laundry and detergent composition
JPS6348399A (en) Tableware detergent containing sodium silicate as builder, cobuilder and active chlorine support agent
AU605573B2 (en) Solid cast warewashing composition
ES2311301T3 (en) DETERGENT COMPOSITIONS AND WATER SOFTENERS.
ES2361070T3 (en) CLEANING PROCEDURE
WO2003045855A1 (en) Cleaning method
EP1935852A1 (en) Water softener composition
EP1776446A1 (en) Method of removing laundry ash
WO2003045856A1 (en) Water-softening tablet
AU2005209457B2 (en) Cleaning method
CA2346402A1 (en) Water-softening and detergent compositions
TW403781B (en) High-density granular detergent composition
LT3599B (en) Utilization amorphous silico aluminate as capture of calcic precipitates
ZA200200550B (en) Water-softening and detergent compositions.
JPH04226200A (en) Non-chlorinated detergent composition for dish washing machine
WO2006005913A1 (en) Method of removing laundry ash
Wirth Organic Polymers in Detergent Formulations
EP1272602A1 (en) Water-softener in powdered form with an effervescent system

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040527

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20050301

17Q First examination report despatched

Effective date: 20050301

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RECKITT BENCKISER N.V.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: DE

Ref legal event code: R081

Ref document number: 60243157

Country of ref document: DE

Owner name: RECKITT BENCKISER CALGON B.V., NL

Free format text: FORMER OWNER: RECKITT BENCKISER N.V., HOOFDDORP, NL

Ref country code: AT

Ref legal event code: REF

Ref document number: 561899

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60243157

Country of ref document: DE

Effective date: 20120809

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2386539

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120822

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 561899

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120613

26N No opposition filed

Effective date: 20130314

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60243157

Country of ref document: DE

Effective date: 20130314

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121130

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120913

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121127

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20151210 AND 20151216

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: RECKITT BENCKISER CALGON B.V.

Effective date: 20160201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 60243157

Country of ref document: DE

Owner name: RECKITT BENCKISER CALGON B.V., NL

Free format text: FORMER OWNER: RECKITT BENCKISER N.V., HOOFDDORP, NL

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: RECKITT BENCKISER N.V., NL

Effective date: 20160225

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20181113

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20181011

Year of fee payment: 17

Ref country code: IT

Payment date: 20181122

Year of fee payment: 17

Ref country code: ES

Payment date: 20181203

Year of fee payment: 17

Ref country code: GB

Payment date: 20181121

Year of fee payment: 17

Ref country code: TR

Payment date: 20181106

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60243157

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191130

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200603

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191127

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191127

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20210531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191127